Indium Phosphide Substrate Manufacturing Method and Epitaxial Wafer Manufacturing Method

ABSTRACT

The present invention affords methods of manufacturing InP substrates, methods of manufacturing epitaxial wafers, InP substrates, and epitaxial wafers whereby deterioration of the electrical characteristics can be kept under control, and at the same time, deterioration of the PL characteristics can be kept under control. An InP substrate manufacturing method of the present invention is provided with the following steps. An InP substrate is prepared (Steps S 1  through S 3 ). The InP substrate is washed with sulfuric acid/hydrogen peroxide (Step S 5 ). After the step of washing with sulfuric acid/hydrogen peroxide (Step S 5 ), the InP substrate is washed with phosphoric acid (Step S 6 ).

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to methods of manufacturing indiumphosphide substrates, to methods of manufacturing epitaxial wafers, toindium phosphide substrates, and to epitaxial wafers.

2. Background Art

Indium phosphide (InP) substrates, on account of features including thatthey possess light-emitting characteristics and that they have a highelectron drift velocity, are widely employed in components includingsemiconductor lasers, LEDs (light-emitting diodes), and high-speedmicroelectronic devices. With semiconductor lasers and LEDs, bymeasuring the PL intensity after the epitaxial layers have been formedonto the InP substrate, an assessment of the light-emitting performancecan be simply and readily made. The PL light-emitting intensity shouldbe strong. And with high-speed devices, since impurities at theinterface between the InP substrate and the epitaxial layers lead toleakage problems, the characteristics stabilize the fewer are n-type orp-type impurities at the interface.

An example of a method of manufacturing InP substrates is disclosed inJapanese Unexamined Pat. App. Pub. No. H05-267185 (Patent Reference 1).Specifically, an ingot is cut into wafers and then the wafers arepolished to a specular finish. The front side of the optically flatwafers, having chemical components of the polishing agents remaining onit, becoming oxidized after the polishing, or having organic matterclinging to it, will have formed thereon a layer (front-side film) thatdiffers from the ingot. Etching removal of the front-side film,employing sulfuric acid, is carried out to leave the thickness of thefront-side film not greater than 1 nm.

Examples, furthermore, of InP substrate front-side treatments employingsolutions other than sulfuric acid are disclosed in Japanese UnexaminedPat. App. Pub. No. H05-166785 (Patent Reference 2), Japanese UnexaminedPat. App. Pub. No. S54-13500 (Patent Reference 3) and JapaneseUnexamined Pat. App. Pub. No. S62-252140 (Patent Reference 4). PatentReference 2 discloses washing InP wafers in a substance blend ofphosphoric acid-hydrogen peroxide-water, or in a liquid blend ofhydrogen fluoride-hydrogen peroxide-water. Patent Reference 3 disclosesetching InP single-crystal wafers with sulfuric acid in which thehydrogen peroxide is at or under 15% by volume. Patent Reference 4discloses washing InP wafers by means a solution blend of phosphoricacid-hydrogen peroxide-water, or a solution blend of hydrogenfluoride-hydrogen peroxide-water.

CITATION LIST Patent Literature

Patent Reference 1: Japanese Unexamined Pat. App. Pub. No. H05-267185

Patent Reference 2: Japanese Unexamined Pat. App. Pub. No. H05-166785

Patent Reference 3: Japanese Unexamined Pat. App. Pub. No. S54-13500

Patent Reference 4: Japanese Unexamined Pat. App. Pub. No. S62-252140

Technical Problem

In above-cited Patent Reference 1, sulfuric acid is employed in order toclear away the front-side film. Consequently, sulfur (S) is leftremaining on the front side by the etching process employing sulfuricacid. A problem with S being residual on the front side is that whenepitaxial layers are formed onto that surface, the electricalcharacteristics are deteriorated.

In above-cited Patent References 2 through 4, InP substrates are washedwith solutions containing hydrogen peroxide.

BRIEF SUMMARY OF THE INVENTION

The present inventors discovered, as a result of dedicated researchefforts, that when solutions containing hydrogen peroxide are employedto wash an InP substrate, silicon (Si) clinging to the front side maynot be sufficiently reduced. They discovered that a problem with Si andother impurities clinging to the front side of an InP substrate is thatwhen epitaxial layers are formed atop the substrate, the electricalcharacteristics deteriorate.

They further discovered that a problem with organic matter beingresidual within the front-side film is that when epitaxial layers areformed atop the substrate, bonding between carbon (C) and oxygen (O),and residual In oxides from temperature ramp-up during epitaxydeteriorate the PL characteristics.

The present invention was brought about in order to resolve issues ofthe kind discussed above, and an object of the present invention is tomake available methods of manufacturing InP substrates, methods ofmanufacturing epitaxial wafers, InP substrates, and epitaxial waferswhereby deterioration of the electrical characteristics can be keptunder control, and at the same time, deterioration of the PLcharacteristics can be kept under control.

Solution to Problem

An InP substrate manufacturing method of the present invention isprovided with the following steps.

An InP substrate is prepared.

The InP substrate is washed with sulfuric acid/hydrogen peroxide.

After the step of washing with sulfuric acid/hydrogen peroxide, the InPsubstrate is washed with phosphoric acid.

On the prepared InP substrate, an organic film from bonding of C andoxygen (O), and an oxide film from bonding of In, P and O will haveformed. In accordance with an InP substrate manufacturing method of thepresent invention, washing with sulfuric acid/hydrogen peroxide, whichcontains strongly acidic sulfuric acid, makes it possible to control theorganic film and oxide film from remaining Deterioration of PLcharacteristics can therefore be kept under control. In that state thenfurther washing with phosphoric acid makes it possible to control S andother impurities in the sulfuric acid/hydrogen peroxide from remainingDeterioration of the electrical characteristics can therefore be keptunder control.

With an above-described method of manufacturing an InP substrate, insaid step of washing with phosphoric acid, preferably an aqueousphosphoric acid solution of concentration that is between 1% and 30%both inclusive is utilized.

The present inventors, as a result of dedicated research efforts,discovered that haze (superficial micro-abrasions) on the front side ofthe InP substrate may be reduced by making the concentration of theaqueous phosphoric acid solution be between 1% and 30%, inclusive.Deterioration of the PL characteristics may therefore be kept undercontrol, and at the same time, deterioration of the electricalcharacteristics may therefore be kept under control and further, haze onthe front side may be reduced.

With an above-described method of manufacturing an InP substrate, insaid preparation step an InP substrate containing a dopant consisting ofat least one substance selected from the group composed of iron (Fe),sulfur (S), tin (Sn), and zinc (Zn) is prepared.

With the present invention, in an aforedescribed-dopant-containing InPsubstrate as well, deterioration of the PL characteristics can be keptunder control and at the same time deterioration of the electricalcharacteristics can be kept under control.

An epitaxial wafer manufacturing method of the present invention isprovided with a step of manufacturing an InP substrate according to anInP substrate manufacturing method of any of the foregoing descriptions,and a step of forming an epitaxial layer onto the InP substrate.

In accordance with an epitaxial wafer manufacturing method of thepresent invention, InP in which the remaining behind of organic filmsand oxide films may be kept under control and in which the remainingbehind of impurities may be minimized is utilized. Therefore, epitaxialwafers in which deterioration of the PL characteristics can be keptunder control and at the same time in which deterioration of theelectrical characteristics can be kept under control can bemanufactured.

An InP substrate of the present invention is an InP substrate having afront side, and is characterized in that along the front side, theconcentration of sulfuric-acid ions (SO₄ ²⁻) is not greater than 0.6ng/cm², and the concentration of C and the concentration of O that hasformed bonds with atoms other than S is 40 atomic percent or less.

In accordance with an InP substrate of the present invention, since theconcentration of sulfuric-acid ions (SO₄ ²⁻) on the front side is notgreater than 0.6 ng/cm², the concentration of impurities is low.Therefore, when an epitaxial layer(s) is formed onto an InP substrate ofthe present invention, deterioration of the electrical characteristicscan be kept under control. Further, the concentration of C and theconcentration of O that has formed bonds with atoms other than S is 40atomic percent or less. Since this keeps organic films and oxide filmsfrom being remnant on the front side, when an epitaxial layer(s) isformed onto an InP substrate of the present invention, deterioration ofthe PL characteristics can be kept under control.

With an aforedescribed InP substrate, preferably it is characterized inthat along the front side the ratio of the In concentration to the Pconcentration (In/P) is 1.23 or less, and In oxides are 1.2 atomicpercent or less.

When In/P is 1.23 or less, the front side is stabilized and bondingtogether with impurities may be kept under control. When the In oxidesare 1.2 atomic percent or less, during temperature ramp-up in order toform epitaxial layers onto the InP substrate, In oxides will fly offmore readily, facilitating the appearance of a cleansed front side.Thus, through the minimizing of front-side impurities, deterioration ofthe PL characteristics may be kept under control.

In the above-described InP, preferably a dopant consisting of at leastone substance selected from the group composed of Fe, S, Sn and Zn isincorporated.

In the present invention, even with an InP substrate containing theabove-described dopant, deterioration of the PL characteristics can bekept under control and at the same time deterioration of the electricalcharacteristics can be kept under control.

An epitaxial wafer of the present invention is furnished with anaforedescribed InP substrate, and an epitaxial layer formed onto thefront side of the InP substrate.

In accordance with an epitaxial wafer of the present invention, an InPsubstrate in which the remaining behind of an organic film may be keptunder control and in which the remaining behind of impurities may bekept under control is utilized. Therefore, an epitaxial wafer in whichdeterioration of the PL characteristics can be kept under control and atthe same time deterioration of the electrical characteristics can bekept under control may be realized.

Advantageous Effects of Invention

In accordance with the foregoing, present-invention methods ofmanufacturing InP substrates, methods of manufacturing epitaxial wafers,InP substrates, and epitaxial wafers make it possible to keepdeterioration of the electrical characteristics under control and at thesame time to keep deterioration of the PL characteristics under control.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a side view representing, in simplified form, an InP substratein Embodying Mode 1 of the present invention.

FIG. 2 is a flowchart setting forth a procedure for manufacturing an InPsubstrate in Embodying Mode 1 of the present invention.

FIG. 3 is a side view representing, in simplified form, an InP substratehaving undergone a slicing operation in Embodying Mode 1 of the presentinvention.

FIG. 4 is a side view representing, in simplified form, an InP substrateafter having been washed with sulfuric acid/hydrogen peroxide inEmbodying Mode 1 of the present invention.

FIG. 5 is a schematic diagram for explaining the state of the front sideof an InP substrate after having been washed with sulfuric acid/hydrogenperoxide in Embodying Mode 1 of the present invention.

FIG. 6 is a schematic diagram for explaining the state of the front sideof an InP substrate in a comparative example.

FIG. 7 is a schematic diagram for explaining the state of the front sideof an InP substrate in a comparative example.

FIG. 8 is a side view representing, in simplified form, an epitaxialwafer in Embodying Mode 2 of the present invention.

FIG. 9 is a flowchart setting forth a procedure for manufacturing anepitaxial wafer in Embodying Mode 2 of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Below, a description of embodying modes and embodiment examples of thepresent invention will be made based on the drawings. It should beunderstood that in the following, identical or corresponding parts inthe drawings are labeled with identical reference marks, and theirdescription will not be repeated.

Embodying Mode 1

Referring to FIG. 1, an explanation of an InP substrate 10 in thepresent embodying mode will be made. As indicated in FIG. 1, the InPsubstrate 10 has a front side 10 a.

Along the front side 10 a, the concentration of SO₄ ²⁻ is not greaterthan 0.6 ng/cm², preferably not greater than 0.05 ng/cm². Since S and Oas impurities clinging to the front side 10 a may be reduced with theconcentration being not greater than 0.6 ng/cm², deterioration of theelectrical characteristics may be kept under control when an epitaxiallayer(s) has been formed onto the InP substrate 10. With theconcentration being not greater than 0.05 ng/cm², deterioration of theelectrical characteristics may be further minimized.

Along the front side 10 a, the concentration of C and the concentrationof O that has formed bonds with atoms other than S is 40 atomic percentor less; preferably it is 37.0 atomic percent or less. With theconcentration being at or below 40 atomic percent, bonds between C andO, which are the organic film, and bonds between In, P and O, which arethe oxide film, may be reduced, whereby deterioration of the PLcharacteristics may be kept under control when an epitaxial layer(s) hasbeen formed onto the InP substrate 10. With the concentration being notgreater than 37.0 atomic percent, deterioration of the PLcharacteristics may be further minimized.

Herein, the foregoing “concentration of C and the concentration of Othat has formed bonds with atoms other than S” can be found by a formulaexpressed by: C concentration+O concentration−S concentration×4. Alongthe front side 10 a, there will be instances in which O has formed bondswith C, In and P, and instances in which O has formed bonds with S.Among the O atoms present on the front side 10 a, the concentration of Othat has formed bonds with atoms other than S serves as an indicator ofthe remaining behind of an organic film and oxide film. That is, O thathas formed bonds with S derives not from the remaining behind of anorganic film and oxide film, but from the sulfuric acid, and is acausative factor in the deterioration of electrical characteristics.Accordingly, to have oxygen be an indicator of the remaining behind ofan organic film, with the formula given above, the O concentration thatis four times the S concentration is excluded in order to omit the Opresent along the front side 10 a as SO₄.

Indium oxides along the front side 10 a preferably are not more than 1.2atomic percent, and more preferably are not more that 1.0 atomicpercent. Indium oxides are difficult to eliminate in forming anepitaxial layer onto the InP substrate 10. Therefore, if In oxides maybe reduced to not more than 1.2 atomic percent, deterioration of the PLcharacteristics can be kept under control. In implementations where itis at or below 1.0 atomic percent, deterioration of the PLcharacteristics can be further minimized.

The ratio of the In concentration to the P concentration (In/P) alongthe front side 10 a preferably is 1.28 or less, and more preferably is1.23 or less. With the ratio being 1.28 or less, P is present to arelatively great extent, whereby the surface stabilizes and thefront-side properties prove to be favorable. The ratio being 1.23 orless lets the front-side properties be more satisfactory.

The aforesaid “concentration of SO₄ ²⁻ on the front side 10 a” is ameasurement determined by ion chromatography. And the aforesaid“concentration of C and concentration of O that has formed bonds withatoms other than S, and In oxides” are measurements determined by x-rayphotoelectron spectroscopy (XPS).

The InP substrate 10 may be constituted from InP, and may contain adopant consisting of at least one substance selected from the groupcomposed of Fe, S, Sn and Zn.

To continue: An explanation of a method in the present embodying mode ofmanufacturing an InP substrate 10 will be made.

To begin with, referring to FIG. 2, an InP ingot is prepared (Step S1).The ingot may be constituted from InP, and may contain a dopantconsisting of at least one substance selected from the group composed ofFe, S, Sn and Zn.

Next, an operation of slicing an InP substrate (InP substrate 11 in FIG.3) from the prepared ingot is carried out (Step S2). The way in whichthe slicing operation is done is not particularly limited. The InPsubstrate will bear a damage layer from the slicing operation.

The InP substrate from the slicing operation is then polished employingpolishing agents, chemical polishing solutions, etc. (Step S3). Thedamage layer due to the slicing operation is thereby removed. These StepS1 through S3 enable the preparation of an InP substrate.

Next, the polished InP substrate is preprocessed (Step S4). Thepolishing agents, chemical polishing solutions, etc. are cleared away bythe preprocessing.

The preprocess washes in an alkaline solution followed by washing inhydrofluoric acid and further washing in an alkaline solution, forexample. After any of Steps S2 through S4, as depicted in FIG. 3 anorganic film and oxide film 12 will have formed on the front side of theInP substrate 11. It will be appreciated that the organic film containsC and O, and that the oxide film contains In, P and O.

Next the InP substrate 11 is washed in sulfuric acid/hydrogen peroxide(Step S5). Sulfuric acid/hydrogen peroxide contains sulfuric acid andaqueous hydrogen peroxide (hydrogen peroxide). As the sulfuricacid/hydrogen peroxide, for example, a solution in which (sulfuricacid:hydrogen peroxide:water)=(10:1:1) to (5:1:1), etc. can be utilized.

Implementing Step S5 makes it possible to reduce, as indicated in FIG.4, the organic film and oxide film 12 having formed on the front side ofthe InP substrate 11. Likewise, Si, etc. clinging to the front side ofthe InP substrate 11 can also be reduced. It will be appreciated that Siwill be contained in the atmosphere, in the water employed in thewashes, and in related media when the InP substrate 10 is manufactured,and thus will have clung to the front side of the InP substrate 11.

Next the InP substrate 11 is washed in phosphoric acid (Step S6).Implementing Step S6 makes it possible to reduce Si, SO₄ ²⁻ (S and O)originating in the sulfuric acid, and other impurities clinging to theInP substrate 11. Further, even in cases where P originating in thephosphoric acid has remained behind on the InP substrate, when P issupplied to the front side 10 a of the InP substrate 10, the surfacebecomes stabilized.

In Step S6 it is preferable that an aqueous phosphoric acid solution ofconcentration that is between 1% and 30%, inclusive be utilized.Front-side haze can thereby be reduced.

Implementing the foregoing steps (Steps S1 through S6) makes it possibleto manufacture the InP substrate represented in FIG. 1.

To continue: An explanation of the effects of a method in the presentembodying mode of manufacturing an InP substrate 10 will be made.Following Step S4 of carrying out the preprocess, as represented in FIG.3 an organic film and oxide film 12, and Si and other impurities willhave adhered to the front side 11 a.

With an InP substrate 10 manufacturing method in the present embodyingmode, as indicated in FIG. 5, the adherence of the organic film andoxide film 12 and of Si will be reduced following Step S5 of the frontside being washed with sulfuric acid/hydrogen peroxide, but the frontside will have clinging to it S originating in the sulfuricacid/hydrogen peroxide. Nevertheless, by virtue of Step S6 of washingwith phosphoric acid, the Si that could not be reduced by Step S5, aswell as the S clinging due to Step S5 can be reduced. That is, theorganic film and oxide film may be reduced, and S, Si and otherimpurities further may be reduced as well. If the organic film and oxidefilm may be reduced, then deterioration of the PL emission intensity (PLcharacteristics) may be kept under control. If the impurities may bereduced, then deterioration in the electrical characteristics may bekept under control. Accordingly, utilizing the InP substrate 10 inwireless communications applications and the like enables thecharacteristics to be improved.

Next an explanation will be made of a comparative example in which,instead of as in Steps S5 and S6, the wash is performed with sulfuricacid as in Patent Reference 1. Since sulfuric acid is more stronglyacidic than sulfuric acid/hydrogen peroxide, Si may be removed to agreater extent, as indicated in FIG. 6, than that following Step S5 ofwashing with sulfuric acid/hydrogen peroxide in the present embodyingmode, but the S residue originating in sulfuric acid is greater.Consequently, with S as an impurity being the cause, the electricalcharacteristics will be harmed.

Furthermore, conceivable is a technique whereby after the substrate hasbeen washed with sulfuric acid, it is washed with phosphoric acid. Inthat case, as indicated in FIG. 7 a portion of the S may be removed, butbecause the S remaining after the substrate has been washed withsulfuric acid is greater than when it has been washed, in the presentembodying mode, with sulfuric acid/hydrogen peroxide, the S residue willbe greater by comparison with the present embodying mode. Consequently,with S as an impurity being the cause, the electrical characteristicswill be harmed.

In addition, the present inventors discovered as a result of dedicatedresearch efforts that if a washing solution containing hydrogen peroxideis employed, as in the above-cited Patent References 2 through 4, to dothe washing, Si cannot be adequately cleared away. Consequently, with Sias an impurity being the cause, the electrical characteristics will beharmed.

An explanation will now be made of a comparative example in which,instead of as in Steps S5 and S6, the wash is performed with phosphoricacid. Since phosphoric acid is a weaker acid than sulfuric acid and moreweakly acidic than sulfuric acid/hydrogen peroxide, its etching oforganic films and oxide films is inadequate. Washing the substrate withphosphoric acid therefore leaves it in a state in which, as indicated inFIG. 3, the organic film and oxide film 12 are left behind.Consequently, with the organic film and oxide film being the cause, thePL characteristics are harmed.

In accordance with the foregoing, the fact that with an InP substratemanufactured according to a method in the present embodying mode ofmanufacturing an InP substrate 10, the organic film and oxide film 12are reduced means that the concentration of C and the concentration of Othat has formed bonds with atoms other than S can be reduced to or below40 atomic percent, while the fact that the impurities are reduced meansthat the concentration of SO₄ ²⁻ can be reduced to or below 0.6 ng/cm².Therefore, when an epitaxial layer(s) has been formed onto the InPsubstrate 10, deterioration of the PL characteristics may be kept undercontrol and at the same time deterioration of the electricalcharacteristics can be kept under control.

Embodying Mode 2

Referring to FIG. 8, an explanation of an epitaxial wafer 20 in thepresent embodying mode will be made.

As represented in FIG. 8, the epitaxial wafer 20 comprises an InPsubstrate 10 of Embodying Mode 1, and an epitaxial layer 21 formed ontothe front side 10 a of the InP substrate 10.

The epitaxial layer 21 may be mono-laminar or multi-laminar.

Along the interface between the InP substrate 10 and the epitaxial layer21, the Si concentration is not greater than 1.8×10¹⁷ atoms/cm³ and theS concentration is not greater than 2×10¹³ atoms/cm³, for example.

To continue: An explanation of a method in the present embodying mode ofmanufacturing an epitaxial wafer 20 will be made. To begin with, asindicated in FIG. 9, an InP substrate 10 is manufactured in conformitywith Embodying Mode 1 (Steps S1 through S6).

Next an epitaxial layer 21 is formed atop the front side 10 a of the InPsubstrate 10 (Step S7). The means whereby the epitaxial layer is formedis not particularly limited; vapor-phase growth methods such as OMVPE(organometallic vapor-phase epitaxy), HVPE (hydride vapor-phaseepitaxy), MBE (molecular beam epitaxy) and sublimation deposition, aswell as liquid-phase growth methods such as flux growth and highnitrogen-pressure solution growth can be adopted.

It should be understood that in Step S7, a plurality of circuit elementsmay be created. In that case, after an epitaxial layer 21 of apredetermined structure has been formed onto the front side 10 a of theInP substrate 10, in order to singulate the InP substrate 10 intoindividual circuit elements, a dividing operation in which, for example,dicing and associated steps are carried out is implemented on thesubstrate.

Implementing the forgoing procedures (Steps S1 through S7) makes itpossible to manufacture the epitaxial wafer 20 represented in FIG. 8.

An epitaxial wafer 20 manufactured in this way is for example mountedonto a leadframe or the like. Then, by implementing a wire-bonding orlike procedure on the package, a semiconductor device utilizing theaforedescribed circuit element can be obtained.

A method in the present embodying mode of manufacturing an epitaxialwafer 20 utilizes an InP substrate 10 of Embodying Mode 1, in which theresidue of the organic film and oxide film has been reduced, and theresidue of impurities has been reduced. An epitaxial wafer 20 in whichdeterioration of the PL characteristics has been kept under control, andin which deterioration of the electrical characteristics has been keptunder control can therefore be manufactured.

In such an epitaxial wafer 20, if the InP substrate 10 contains a dopantconsisting of at least one substance selected from the group composed ofFe, S, Sn and Zn, it will have the following effects.

If the dopant is Fe, its concentration will be, for example, from 1×10¹⁶atoms/cc to 1×10¹⁷ atoms/cc, and the electrical characteristics will besemi-insulating. In that case, if the concentration of Si and S at theinterface between the InP substrate 10 and the epitaxial layer 21 ishigh, abnormalities in the electrical characteristics (leakage) willoccur. Nevertheless, because the present embodying mode makes forreduction of the Si and S concentration, the epitaxial wafer is ideallysuited to utilization in such devices as HEMTs (high electron mobilitytransistors) and HBTs (heterojunction bipolar transistors).

If the dopant is S, its concentration will be, for example, from0.5×10¹⁸ atoms/cc to 8×10¹⁸ atoms/cc, and the electrical characteristicswill be n-type. In that case, if the concentration of O and C at theinterface between the InP substrate 10 and the epitaxial layer 21 ishigh, abnormalities in the electrical characteristics and degradation ofthe optical emission intensity will occur. Nevertheless, because thepresent embodying mode makes for reduction of the O and C concentration,the epitaxial wafer is ideally suited to utilization in lasers and likedevices. And in implementations in which haze may be reduced, theemission intensity furthermore can be improved.

If the dopant is Sn, its concentration will be, for example, from 1×10¹⁸atoms/cc to 6×10¹⁸ atoms/cc, and the electrical characteristics will ben-type. In that case, if the concentration of O and C at the interfacebetween the InP substrate 10 and the epitaxial layer 21 is high,abnormalities in the electrical characteristics and degradation of theoptical emission intensity will occur. Nevertheless, because the presentembodying mode makes for reduction of the O and C concentration, theepitaxial wafer is ideally suited to utilization in lasers and likedevices. And in implementations in which haze may be reduced, theemission intensity furthermore can be improved.

If the dopant is Zn, its concentration will be, for example, from 3×10¹⁸atoms/cc to 8×10¹⁸ atoms/cc, and the electrical characteristics will bep-type. In that case, if the concentration of Si and S at the interfacebetween the InP substrate 10 and the epitaxial layer 21 is high,abnormalities in the electrical characteristics and degradation of theoptical emission intensity will occur. Nevertheless, because the presentembodying mode makes for reduction of the Si and S concentration, theepitaxial wafer is ideally suited to utilization in lasers and likedevices. And in implementations in which haze may be reduced, theemission intensity furthermore can be improved.

Embodiment 1

In the present embodiment, the effects from the provision of a step ofwashing with sulfuric acid/hydrogen peroxide and a step of washing withphosphoric acid were investigated.

PRESENT INVENTION EXAMPLE 1

The method of Present Invention Example 1 of manufacturing an InPsubstrate was basically the same as that of Embodying Mode 1.Specifically, to begin with an InP crystal ingot was grown by thevertical Bridgman technique (Step S1). A slicing operation was thencarried out on the ingot (Step S2). Next, polishing employing apolishing solution containing a polishing agent, an oxidizer, and a pHadjuster, and in which the pH was between 2 and 4, inclusive, wasperformed (Step S3). Colloidal silica having grain sizes in which thegrain diameter was from 3 nm to 30 nm was employed as the polishingagent. Trichloroisocyanuric acid was employed as the oxidizer. Malicacid was employed as the pH adjuster. An InP substrate was therebyprepared.

Next a preprocess was carried out (Step S4). For the preprocess, washingin an alkaline solution, washing in a hydrofluoric acid, and washing inan alkaline solution were carried out, in that order.

Next, the InP substrate was washed in sulfuric acid/hydrogen peroxide(Step S5). The sulfuric acid/hydrogen peroxide was sulfuricacid:hydrogen peroxide:water=10:1:1. And the wash was carried out atroom temperature. After that the substrate was rinsed in running waterfor 10 minutes.

Subsequently, the InP substrate was washed in phosphoric acid (Step S6).The concentration of the phosphoric acid was 30%. Following that, thesubstrate was given a running-water rinse for 10 minutes and afterwardsunderwent centrifugal drying. Here, the drying may be evaporativedesiccation by means of alcohol. An InP substrate 10 of PresentInvention Example 1 was thereby manufactured.

COMPARATIVE EXAMPLES 1 THROUGH 8

The method of manufacturing the InP substrates of Comparative Examples 1through 8 was basically the same as that of Present Invention Example 1,but in a replacement of Steps S5 and S6, the washing solutions enteredin Table I below were used.

Measurement Method

The front-side composition of the InP substrates of Present InventionExample 1 and Comparative Examples 1 through 8 was characterized by XPSanalysis. A PHI Quantum 2000 was employed as the device for themeasurement. The analysis parameters were as follows. Monochromatic AlKαphotons having an energy of 1486.6 eV were employed as the x-ray source.The photoelectron ejection angle was put at 30°. The analysis area wasmade 1400 μm×300 μm. For the charge referencing a correction with the Cis line of the C—H binding energy being 284.8 eV was carried out. Theresults are set forth in Table I below.

In addition, from the front-side composition of the InP substrates, theratio of In to P (In/P) was found. Those results are set forth in TableI below.

TABLE I Surface composition (atomic %) Surface Surface C + O −composition (ng/cm²) atomic ratio Wash solution In P C O S S × 4 Inoxides SO₄ ²⁻ In/P Pres. Invent. Sulfuric acid/hydrogen peroxide(10:1:1) 34.8 28.3 16.8 20.2 0 37.0 1.03 0.05 1.23 Ex. 1 → phosphoricacid (30%) Comp. Ex. 1 Sulfuric acid (96%) 28.5 22.3 20.6 26.3 2.3 37.70.53 1.6 1.28 Comp. Ex. 2 Sulfuric acid/hydrogen peroxide (10:1:1) 29.323.1 21.1 25.8 0.7 44.1 0.8 0.07 1.27 Comp. Ex. 3 Hydrochloric acid (5%)30.5 22.0 20.9 26.6 0 47.5 2.0 0.05 1.39 Comp. Ex. 4 Hydrofluoric acid(30%) 30.3 22.8 24.4 22.7 0 47.1 1.75 0.05 1.33 Comp. Ex. 5 Hydrofluoricacid/hydrogen peroxide 29.5 22.4 25.5 22.6 0 48.1 1.5 0.07 1.32 (10:1:1)Comp. Ex. 6 Nitric acid (30%) 29.0 22.4 26.1 22.5 0 48.6 1.5 0.06 1.29Comp. Ex. 7 Phosphoric acid (30%) 32.7 25.4 18.5 23.4 0 41.9 0.87 0.051.29 Comp. Ex. 8 Sulfuric acid (96%) 33.1 27.2 16.3 20.9 2.5 27.2 0.51.5 1.22 → phosphoric acid (30%)

Measurement Results

As indicated in Table I, with the InP substrate of Present InventionExample 1, which was washed with sulfuric acid/hydrogen peroxide andthereafter was washed with phosphoric acid, the concentration ofsulfuric acid ions, which constituted impurities, was not greater than0.6 ng/cm², while the concentration of O having formed bonds with C,which constituted an organic film, and the concentration of C was notgreater than 40 atomic percent. It was therefore understood that withthe front side of the InP substrate of Present Invention Example 1,impurities had been reduced, and the organic film and oxide film hadbeen reduced as well.

Further, because it had been washed with phosphoric acid, the InPsubstrate of Present Invention Example 1 had a stabilized surface inwhich the front-side atomic ratio (In/P) 1.28 or less. Moreover, withthe InP substrate of Present Invention Example 1, the In oxides could bereduced to no more than 1.2%.

On the other hand, with Comparative Example 1, which had been washedwith sulfuric acid, and Comparative Example 8, which had been washedwith phosphoric acid upon having been washed with sulfuric acid, theconcentration of SO₄ ²⁻ exceeded 0.6 ng/cm². From these facts it wasunderstood that S deriving from sulfuric acid had remained on the InPsubstrate to a considerable extent.

And in Comparative Example 2 through Comparative Example 7, in whichacids weaker than sulfuric acid were employed, the concentration of Cand the concentration of O having formed bonds with atoms other than Sexceeded 40 atomic percent. From these facts it was understood that anorganic film and oxide film had remained on the InP substrate to aconsiderable extent.

From the foregoing, it could be confirmed that providing, according tothe present embodiment, the step of washing with sulfuric acid/hydrogenperoxide and the step of washing with phosphoric acid made possiblebeing able to reduce the residue of organic film to the same level as incases where sulfuric acid is employed, and further made possiblereducing the residue of impurities.

Also, it was understood that by providing the step of washing withsulfuric acid/hydrogen peroxide and the step of washing with phosphoricacid, an InP substrate may be realized in which the concentration of SO₄²⁻ was at or below 0.6 ng/cm², and the concentration of C and theconcentration of O having formed bonds with atoms other than S was at orbelow 40 atomic percent.

It will be appreciated that in Present Invention Example 1, theconcentration of SO₄ ²⁻ in the InP substrate was 0.05 ng/cm², and theconcentration of C and the concentration of O having formed bonds withatoms other than S was 37 atomic percent. The present inventors gainedthe insight, resulting from dedicated research efforts, that in respectof the SO₄ ²⁻ concentration, a margin of error of some 0.55 ng/cm²arises, while in respect of the concentration of C and the concentrationof O having formed bonds with C, a margin of error of some 3 atomicpercent arises. Consequently, in the present invention, allowing for afactor of safety with respect to the figures obtained in PresentInvention Example 1, the threshold for the SO₄ ²⁻ concentration is putat not greater than 0.6 ng/cm², while the threshold for theconcentration of C and the concentration of O having formed bonds withatoms other than S is put at not greater than 40 atomic percent.

Embodiment 2

In the present embodiment, the effects of creating an epitaxial layerutilizing an InP substrate with respect to which a step of washing withsulfuric acid/hydrogen peroxide and a step of washing with phosphoricacid have been provided were investigated.

The following epitaxial layers were formed onto the InP substrates ofPresent Invention Example 1 and of Comparative Examples 1 through 8. AnInP layer having a thickness of 300 nm was formed by an OMVPE techniqueonto the InP substrates.

Onto the InP layer, an InGaAs layer having a thickness of 5 nm wasformed by an OMVPE technique. Onto the InGaAs layer, an InP layer havinga thickness of 300 nm was formed by an OMVPE technique. Epitaxial wafersof Present Invention Example 1 and Comparative Examples 1 through 8 werethereby manufactured.

Measurement Method

In respect of the epitaxial wafers of Present Invention Example 1 andComparative Examples 1 through 8, the PL intensity of the InGaAs layerwas measured by a PL intensity measurement method with the followingparameters. The excitation beam wavelength was 532 nm. The measurementwavelength was from 1250 nm to 1500 nm. For the measuring machine, a PLM150 manufactured by Nanometrics Inc. was employed. The results are setforth in Table II below.

With further regard to the epitaxial wafers of Present Invention Example1 and Comparative Examples 1 through 8, the Si concentration and Sconcentration at the interface between the epitaxial layers and the InPsubstrate were measured by SIMS. Those results are set forth in Table IIbelow. Here, in Table II, “ND” indicates that because the concentrationwas below the detection bottom limit (2×10¹³ atoms/cm³), it was notdetected.

TABLE II Wash solution PL intensity (a.u.) Si (atomic/cm³) S(atomic/cm³) Pres. Invent. Sulfuric acid/hydrogen peroxide (10:1:1) 81.81.80 × 10¹⁷ ND Ex. 1 → phosphoric acid (30%) Comp. Ex. 1 Sulfuric acid(96%) 77.4 1.61 × 10¹⁷ 8.16 × 10¹⁶ Comp. Ex. 2 Sulfuric acid/hydrogenperoxide (10:1:1) 75.0 7.54 × 10¹⁷ ND Comp. Ex. 3 Hydrochloric acid (5%)56.0 7.38 × 10¹⁷ ND Comp. Ex. 4 Hydrofluoric acid (30%) 59.0 6.22 × 10¹⁷ND Comp. Ex. 5 Hydrofluoric acid/hydrogen peroxide 60.0 8.46 × 10¹⁷ ND(10:1:1) Comp. Ex. 6 Nitric acid (30%) 61.0 9.28 × 10¹⁷ ND Comp. Ex. 7Phosphoric acid (30%) 63.2 1.91 × 10¹⁷ ND Comp. Ex. 8 Sulfuric acid(96%) 83.4 1.74 × 10¹⁷ 9.41 × 10¹⁵ → phosphoric acid (30%)

Measurement Results

As indicated in Table II, with the epitaxial wafer of Present InventionExample 1, furnished with an InP substrate that had been washed withsulfuric acid/hydrogen peroxide and thereafter had been washed withphosphoric acid, with the PL intensity being at least 80 (a.u.), the Plcharacteristics could be kept from deteriorating. Moreover, theepitaxial wafer of Present Invention Example 1 had a low Siconcentration of not greater than 2×10¹⁷ atoms/cm³, and a low Sconcentration that was below the detection bottom limit. From thesefacts it was understood that the impurity concentration at the interfacebetween the InP substrate and the epitaxial layers could be reduced. Andit was understood that therefore the electrical characteristics could bekept from deteriorating.

On the other hand, in Comparative Example 1, in which an InP substratethat had been washed with sulfuric acid was employed, and in ComparativeExample 8, in which an InP substrate that had been washed withphosphoric acid upon having been washed with sulfuric acid was employed,strongly acidic sulfuric acid was used. Inasmuch the organic film andoxide film could therefore be reduced, deterioration of the PL intensitycould be kept under control, and the concentration of Si as an impuritycould be reduced. It was understood, however, that in the interfacebetween the InP substrate and the epitaxial layers, S deriving from thesulfuric acid remained to a considerable extent. It was understood thatowing to these factors, deterioration of the electrical characteristicsarose.

And in Comparative Example 2 through Comparative Example 7, employingInP substrates in which acids of weaker acidity than sulfuric acid wereused, since sulfuric acid was not employed, the S concentration could bereduced. Yet since the organic film and oxide film could not beadequately reduced, the PL intensity was low. Further, it was understoodthat at the interface between the InP substrate and the epitaxial layerSi as an impurity remained to a considerable extent. It was understoodthat deterioration of the electrical characteristics arose from thesefactors.

Furthermore, when Comparative Example 1, which had been washed withsulfuric acid, and Comparative Example 2, which had been washed with awashing solution containing sulfuric acid and hydrogen peroxide, werecompared, it was understood that on account of the solution's containinghydrogen peroxide, Si present at the interface could not be adequatelycleared away. With Present Invention Example 1, while sulfuricacid/hydrogen peroxide was utilized, the Si that could not besufficiently reduced with the sulfuric acid/hydrogen peroxide wasfurther reduced with phosphoric acid, whereby the Si concentration couldbe reduced down to the same level as with sulfuric acid.

From the foregoing, it could be confirmed that by providing, accordingto the present embodiment, the step of washing with sulfuricacid/hydrogen peroxide and the step of washing with phosphoric acid,deterioration of the PL intensity could be minimized to the same levelas in cases where sulfuric acid is employed, and furthermore, it waspossible to kept the electrical characteristics from deteriorating.

Embodiment 3

In the present embodiment, the effects of washing with phosphoric acidof concentration that is between 1% and 30%, inclusive, wereinvestigated.

PRESENT INVENTION EXAMPLES 2 THROUGH 5

The InP substrates and epitaxial wafers of Present Invention Examples 2through 5 were manufactured in basically the same way as with PresentInvention Example 1, but differed in that in Step S6 of washing withphosphoric acid, phosphoric acid of the concentrations entered in TableIII below was utilized.

Measurement Method

The organic film thickness and the haze on the front side of the InPsubstrates, as well as the haze on the epitaxial layers, of PresentInvention Examples 1 through 5 were measured. An Auto EL IVEllipsometer, manufactured by Rudolph Research Analytical, was employedto measure the organic film thickness. A 6220 Surfscan Wafer SurfaceInspection System, manufactured by KLA-Tencor Corporation was employedto measure the haze. These results are set forth in Table III below.

TABLE III Organic Epitaxial Phosphoric film InP substrate layer acidconc. thickness haze haze (%) (Å) (ppm) (ppm) Pres. Invent. Ex. 2 1%5.20 1.26 1.35 Pres. Invent. Ex. 3 5% 4.94 1.15 1.23 Pres. Invent. Ex. 130% 4.60 1.22 1.67 Pres. Invent. Ex. 4 50% 2.67 1.95 2.40 Pres. Invent.Ex. 5 85% 5.00 1.93 2.39

Measurement Results

As indicated in Table III, with Present Invention Examples 1 through 3,in which the phosphoric acid concentration was from 1% to 30%, haze inthe InP substrates and haze in the epitaxial wafers was diminished. Itwas understood that because the front-side roughness of the InPsubstrates was minuscule, the morphology of the epitaxial wafers hadameliorated.

From the foregoing, it was understood that by washing, according to thepresent embodiment, with phosphoric acid of from 1% to 30%concentration, haze on the front side of InP substrates and epitaxialwafers may be reduced.

The presently disclosed embodying modes and embodiment examples shouldin all respects be considered to be illustrative and not limiting. Thescope of the present invention is set forth not by the above-describedembodying modes but by the scope of the patent claims, and is intendedto include meanings equivalent to the scope of the patent claims and allmodifications within the scope.

REFERENCE SIGNS LIST

10, 11: InP substrate; 10 a, 11 a: front side; 12: organic film andoxide film; 20: epitaxial wafer; 21: epitaxial layer

What is claimed is:
 1. An indium phosphide substrate manufacturingmethod comprising: a step of preparing an indium phosphide substrate; astep of washing the indium phosphide substrate with sulfuricacid/hydrogen peroxide; and a step, following said step of washing withsulfuric acid/hydrogen peroxide, of washing the indium phosphidesubstrate with phosphoric acid.
 2. The indium phosphide substratemanufacturing method set forth in claim 1, wherein in said step ofwashing with phosphoric acid, a aqueous phosphoric acid solution havinga concentration of from 1% to 30%, inclusive, is utilized.
 3. The indiumphosphide substrate manufacturing method set forth in claim 1, whereinin said preparation step an indium phosphide substrate containing adopant consisting of at least one substance selected from the groupcomposed of iron, sulfur, tin, and zinc is prepared.
 4. An epitaxialwafer manufacturing method comprising: a step of manufacturing an indiumphosphide substrate according to the indium phosphide substratemanufacturing method set forth in any one of claim 1; and a step offorming an epitaxial layer onto the indium phosphide substrate.